CN101941692B - Preparation method of high-crystallinity double-walled carbon nano tube - Google Patents
Preparation method of high-crystallinity double-walled carbon nano tube Download PDFInfo
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- CN101941692B CN101941692B CN2010102910357A CN201010291035A CN101941692B CN 101941692 B CN101941692 B CN 101941692B CN 2010102910357 A CN2010102910357 A CN 2010102910357A CN 201010291035 A CN201010291035 A CN 201010291035A CN 101941692 B CN101941692 B CN 101941692B
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Abstract
The invention relates to a preparation method of a high-crystallinity double-walled carbon nano tube, belonging to the technical field of preparation processes of carbon nano tube materials. The preparation method is characterized in that the carbon nano tube is prepared by adopting an anodic carbon electrode bar containing an iron catalyst and realizing the arc discharge between a negative electrode and a positive electrode by using an arc discharging method under a discharging atmosphere of hydrogen or mixed gas of hydrogen and argon, and meanwhile, the double-walled carbon nano tube is purified under the high-temperature treatment of hydrogen and air so as to finally obtain the double-walled carbon nano tube with purity above 90 percent. The prepared double-walled carbon nano tube has the advantages of high crystallinity, narrow caliber distribution, small average diameter and high purity.
Description
Technical field
The present invention relates to a kind of preparation method of high crystalline double-walled carbon nano-tube, belong to carbon nano-tube material fabricating technology field.
Background technology
Double-walled carbon nano-tube is a kind of of multi-walled carbon nano-tubes, is SWCN a type to the multi-walled carbon nano-tubes transit time, is the simplest multi-walled carbon nano-tubes.Because the diameter of double-walled carbon nano-tube approaches SWCN, and the electricity of double-walled carbon nano-tube, optics, mechanical property also approach SWCN, it also has the advantage of multi-walled carbon nano-tubes concurrently simultaneously simultaneously.For example: double-walled carbon nano-tube has the wearing quality and the scale resistance of similar multi-walled carbon nano-tubes, can show the electricity the same with SWCN, optics, mechanics and quantum effect characteristic simultaneously.Therefore; In recent years; Double-walled carbon nano-tube begins to substitute gradually SWCN and multi-walled carbon nano-tubes, becomes the active material of practical applications such as a ballistic transistor, transparent conductive film, multi-functional composite reinforcing material, molecular electronic device, biochemical sensor.
1991, and the multi-walled carbon nano-tubes that the Sumio Iijima discovery is prepared by arc process (Ii jima S et al.Nature, 1991,354:56-58).Sumio Iijima in 1993 utilize again arc process prepared SWCN (Ii jima S et al.Nature, 1993,363:603-605).But, up to calendar year 2001, just by Hutchison utilize the hydrogen arc process prepare the sample of enrichment double-walled carbon nano-tube (Hutchison JL et al.Carbon, 2001,39:761-770).This sample mainly is present in around the electrode, and comparatively small amt can't mass preparation.The people such as Cheng Huiming of physics of metals institute (Li LX et al.Carbon, 2005,43:623-629) utilize arc process to prepare double-walled carbon nano-tube, but the diameter Distribution of double-walled carbon nano-tube is very wide, and needs multi-walled carbon nano-tubes as raw material.People such as the former allusion quotation of a specified duration of formal little slender bamboo (Sugai T et al.Nano Letters, 2003,3(6): 769-773) utilize the high temperature pulse arc process to prepare the narrower double-walled carbon nano-tube sample of diameter Distribution, but the output of preparation is very low, can't large-scale production.Wei advances congruent people (Wei et al.Journal of Physical Chemistry B; 2004; 108 (26): 8844-8847) utilize chemical Vapor deposition process to prepare the double-walled carbon nano-tube sample; But because the limitation of chemical Vapor deposition process own, high not enough by the crystallinity of the carbon nanotube of the relative arc process preparation of crystallinity of the carbon nanotube of this method preparation, and the diameter Distribution of double-walled carbon nano-tube is very wide.Therefore, need to seek a kind of highly purified double-walled carbon nano-tube of high crystalline of both can having prepared, also will keep double-walled carbon nano-tube that less diameter Distribution is arranged, and be applicable to fairly large preparation.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of double-walled carbon nano-tube of high crystalline
The preparation method of a kind of high crystalline double-walled carbon nano-tube of the present invention is characterized in that having following preparation process and step:
A. the preparation of iron-containing catalyst anode carbon electrode bar: but adopt the greying carbon dust is raw material, mixes mass percent and is respectively 4% iron catalyst and 0.5% sulphur cocatalyst, is suppressed into cylindrical squarely rod then; In 800-1200 ℃ of oxygen deficient atmospheres, carry out sintering, and then in 1400-2000 ℃ of oxygen deficient atmospheres, carry out sintering;
B. the preparation of carbon nanotube: utilize arc discharge method to prepare; Utilize above-mentioned iron content sulfur-bearing catalyst carbon electrode bar to be anode; With the high purity graphite rod is negative electrode; Be under the discharge atmosphere of mixed gas of hydrogen or hydrogen and argon gas of 39900～66500Pa at air pressure, realize that the arc-over between positive and negative the two poles of the earth makes carbon nanotube; Discharging current is 50～200A; Distance during discharge between negative electrode and the anode is 2～4mm;
C. the purification of double-walled carbon nano-tube: in hydrogen and air atmosphere, carry out earlier high-temperature heat treatment; The temperature of hydrogen atmosphere is controlled at 700～900 ℃; The temperature of air atmosphere is controlled at 400～500 ℃, and 0.5～1.0 hour treatment time is to remove most carbon impurity; Secondly soak with concentrated hydrochloric acid, stir or reflow treatment, this step is to remove most metal catalyst particles; Utilize hydrogen and air under comparatively high temps, to heat-treat at last again; The treatment temp of hydrogen is controlled at 900～1100 ℃; The temperature of air atmosphere is controlled at 450～550 ℃; This step can be removed most residual carbon impurity and produced simultaneously SWCN; Finally obtain containing the carbon nanotube of double-walled carbon nano-tube more than 90%, promptly the purity of double-walled carbon nano-tube reaches more than 90%.
The above-mentioned arc discharge method that utilizes prepares the mixed gas that carbon nanotube is described hydrogen and argon gas, and both volume ratios are 1: 1～4: 1.
Characteristics of the present invention and advantage are described below:
Adopted iron to make catalyzer among the present invention and sulphur is made cocatalyst, the effect that adds iron is the vegetative point that it can be used as carbon nanotube, causes the growth of carbon nanotube; The existence of sulphur can change the diameter of carbon nanotube, improves the production rate of double-walled carbon nano-tube, promptly improves the relative ratio of double-walled carbon nano-tube and SWCN.
The double-walled carbon nano-tube that the inventive method is prepared has crystallinity height, caliber narrowly distributing, mean diameter is little and purity is high advantage.
Description of drawings
Sem (SEM) photo of the double-walled carbon nano-tube that Fig. 1 prepares for the present invention
Transmission electron microscope (TEM) photo of the double-walled carbon nano-tube that Fig. 2 prepares for the present invention
High resolution transmission electron microscope (HRTEM) photo of the double-walled carbon nano-tube that Fig. 3 prepares for the present invention
Raman spectrum (Raman spectrum) result of the double-walled carbon nano-tube that Fig. 4 prepares for the present invention
Thermogravimetric analysis (the TGA and DTG) result of the double-walled carbon nano-tube that Fig. 5 prepares for the present invention
Embodiment
After specific embodiment of the present invention being described at present.
In the present embodiment, the preparation process and the step of double-walled carbon nano-tube are described below:
(1) anode contains the preparation of catalyst carbon electrode bar
But adopting the greying carbon dust is raw material; Mix mass percent and be respectively 1% iron catalyst and 0.5% sulphur cocatalyst, be pressed into cylindrical or square bar then; Sintering in 800-1200 ℃ of oxygen deficient atmospheres, and then in 1400-2000 ℃ of oxygen deficient atmospheres sintering.
(2) preparation of carbon nanotube
Utilize the preparation of direct current arc electric discharge.Negative electrode is the high purity graphite rod, and anode is for containing the catalyst carbon electrode bar, and discharge atmosphere is that hydrogen perhaps accounts for hydrogen and the argon gas mixed gas that volume(tric)fraction is 50%-80% for hydrogen.Discharging current is 50 amperes to 200 amperes.During discharge, the distance between anode and the negative electrode remains between 2 millimeters to 4 millimeters.
(3) purification of double-walled carbon nano-tube
The carbon nanotube sample of preparing contains carbon impurity such as granules of catalyst and decolorizing carbon; Also have the part SWCN to generate; This just need carry out purification processes to the carbon nanotube sample, comprises to remove metal catalyst and carbon impurity, and removes the part SWCN that generates.At first, utilize hydrogen (temperature is controlled at 700-900 ℃) and air (temperature is controlled at 400-500 ℃) pyroprocessing carbon nanotube 0.5～1.0 hour, this step can be removed most of carbon impurity.Secondly, utilize concentrated hydrochloric acid immersion, stirring or reflow treatment carbon nanotube, this step can be removed most metal catalyst particles.At last, utilize hydrogen (temperature is controlled at 900-1100 ℃) and air (temperature is controlled at 450-550 ℃) pyroprocessing carbon nanotube, this step can be removed most residual carbon impurity and SWCN.Finally obtain purity more than 90%, promptly contain the double-walled carbon nano-tube sample of double-walled carbon nano-tube more than 90%.
Instrument detecting
Referring to Fig. 1, Fig. 2 and Fig. 3.
Sem and transmission electron microscope observation show that the carbon nanotube sample has very high purity.The statistics of high resolution transmission electron microscope provides and is double-walled carbon nano-tube in the carbon nanotube sample more than 90%.The statistics of high resolution transmission electron microscope and raman spectroscopy measurement show that the diameter Distribution of double-walled carbon nano-tube is very narrow, and the internal diameter majority is distributed between the 0.7-0.9nm.
Referring to Fig. 4 and Fig. 5.
Fig. 4 is the Raman spectrogram of double-walled carbon nano-tube for Raman spectrum.Through analyzing G-band (1585cm-1) is that G peak and D-band (1311cm-1) are the ratio (I at D peak
G/ I
D=14.3) and Electronic Speculum picture (Fig. 1,2 and 3), can infer, the carbon nanotube good crystallinity that this preparation method prepares, defect and impurity is less.Through analyzing RBM (100-300cm-1) is climacteric; Can judge prepared carbon nanotube is double-walled carbon nano-tube; Bring formula into through the position of two peak values and can calculate the internal diameter of representing double-walled carbon nano-tube respectively and the diameter of external diameter, be respectively 0.9nm and 1.6nm, because have only tangible two peaks strong very high bimodal; Combine the direct observation (Fig. 3) of transmission electron microscope again, so it is narrow to draw prepared double-walled carbon nano-tube diameter Distribution.
Fig. 5 is thermogravimetric analysis figure.Can find out through thermogravimetric analysis figure, after temperature arrives 850 degree, below the downgrade to 90%; Carbon content reaches more than 90% in the interpret sample; Combine the partial heat multigraph in Fig. 5 illustration to find out again, the carbon foreign matter content in the sample is shared few, in other words; The content of carbon nanotube reaches 90% in the sample, has higher purity.In addition; In the differential thermogravimetric, can see a tangible peak, the pairing temperature in this peak is 755 degrees centigrade and represents maximum oxidation consumption temperature; This is very high temperature, and the double-walled carbon nano-tube of general preparation method such as chemical Vapor deposition process preparation can not reach so high temperature.Explain that prepared double-walled carbon nano-tube sample has very high crystallinity and oxidation-resistance.
Claims (2)
1. the preparation method of a high crystalline double-walled carbon nano-tube is characterized in that having following preparation process and step:
A. the preparation of iron-containing catalyst anode carbon electrode bar: but adopt the greying carbon dust is raw material, mixes mass percent and is respectively 1% iron catalyst and 0.5% sulphur cocatalyst, is pressed into cylindrical or square bar then; In 800-1200 ℃ of oxygen deficient atmospheres, carry out sintering, and then in 1400-2000 ℃ of oxygen deficient atmospheres sintering;
B. the preparation of carbon nanotube: utilize arc discharge method to prepare; Adopting above-mentioned iron content sulfur-bearing catalyst carbon electrode bar is anode; With the high purity graphite rod is negative electrode; Be under the discharge atmosphere of mixed gas of hydrogen or hydrogen and argon gas of 39900～66500Pa at air pressure, realize the arc-over between positive and negative two electrodes, make carbon nanotube; Discharging current is 50～200A; Distance during discharge between anode and the negative electrode is 2～4mm;
C. the purification of double-walled carbon nano-tube: in hydrogen and air atmosphere, carry out earlier high-temperature heat treatment; The temperature of hydrogen atmosphere is controlled at 700～900 ℃; The temperature of air atmosphere is controlled at 400～500 ℃, and the treatment time is 0.5～1.0 hour, to remove most carbon impurity; Secondly with concentrated acid immersion, stirring or reflow treatment, this step can be removed most metal catalyst particles; Utilize hydrogen and air under comparatively high temps, to heat-treat at last again; The treatment temp of hydrogen is controlled at 900～1100 ℃; The temperature of air atmosphere is controlled at 450～550 ℃; This step can be removed most residual carbon impurity and produced simultaneously SWCN; Finally obtain containing the carbon nanotube of double-walled carbon nano-tube more than 90%, promptly the purity of double-walled carbon nano-tube reaches more than 90%.
2. the preparation method of a kind of high crystalline double-walled carbon nano-tube as claimed in claim 1 is characterized in that: the mixed gas of described hydrogen and argon gas when utilizing arc discharge method to prepare carbon nanotube, both volume ratios are 1: 1～4: 1.
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| CN102730666A (en) * | 2011-04-15 | 2012-10-17 | 上海大学 | Method for preparing carbon nano-wires |
| CN106120296B (en) * | 2016-06-21 | 2018-09-11 | 郑州大学 | A kind of carbon nano-tube fibre purification process |
| JPWO2020195800A1 (en) * | 2019-03-27 | 2020-10-01 | ||
| CN110451543A (en) * | 2019-09-01 | 2019-11-15 | 浙江理工大学 | A kind of preparation method based on carbon nano tube modified modified quicklime desiccant |
| CN113675387A (en) * | 2021-07-15 | 2021-11-19 | 南京信息工程大学 | Sulfur-carbon composite material, preparation method and application thereof |
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| CN101549863A (en) * | 2008-04-02 | 2009-10-07 | 中国科学院金属研究所 | Preparation method of double-wall carbon nano-tube with good thermal stability |
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| JP3754417B2 (en) * | 2000-10-06 | 2006-03-15 | フラーレン インターナショナル コーポレイション | Double-walled carbon nanotubes and methods for their production and use |
| WO2006007760A1 (en) * | 2004-07-19 | 2006-01-26 | Lingyong Kong | Double-walled carbon nanotubes and the preparing method of same |
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| CN1506304A (en) * | 2002-12-10 | 2004-06-23 | 中国科学院金属研究所 | Prepn of very long directional carbon nanotube and carbon nanotube rope with controllable layer number |
| CN1456498A (en) * | 2003-06-09 | 2003-11-19 | 清华大学 | Synthesis of double walled carbon nano-tubes |
| CN1743265A (en) * | 2004-08-31 | 2006-03-08 | 中国科学院金属研究所 | A kind of low-cost preparation method of double-wall carbon nano-tube |
| CN101549863A (en) * | 2008-04-02 | 2009-10-07 | 中国科学院金属研究所 | Preparation method of double-wall carbon nano-tube with good thermal stability |
Non-Patent Citations (4)
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